In the last 10 years, we have witnessed an extensive development of instrumental techniques in analytical methods for determination of various molecules and ions at very low concentrations. Nevertheless, the presence of interfering components of complex samples hampered the applicability of new analytical strategies. Thus, additional sample pre-treatment steps were proposed to overcome the problem. Solid sorbents were used for clean-up samples but insufficient selectivity of commercial materials limited their utility. Here, the application of molecularly imprinted polymers (MIPs) or ion-imprinted polymers (IIPs) in the separation processes have recently attracted attention due to their many advantages, such as high selectivity, robustness, and low costs of the fabrication process. Bulk or monoliths, microspheres and core-shell materials, magnetically susceptible and stir-bar imprinted materials are applicable to different modes of solid-phase extraction to determine target analytes and ions in a very complex environment such as blood, urine, soil, or food. The capability to perform a specific separation of enantiomers is a substantial advantage in clinical analysis. The ion-imprinted sorbents gained interest in trace analysis of pollutants in environmental samples. In this review, the current synthetic approaches for the preparation of MIPs and IIPs are comprehensively discussed together with a detailed characterization of respective materials. Furthermore, the use of sorbents in environmental, food, and biomedical analyses will be emphasized to point out current limits and highlight the future prospects for further development in the field.

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It this paper, the comprehensive design process was carried out to fabricate selective, molecularly imprinted polymer (MIP). The material was used as a sorbent in the optimized analytical method, aimed at verifying the hypothesis that the conditions of an analytical process could convert 4-hydroxyphenylacetic acid to 4-hydro-3-nitrophenylacetic acid, comprising a series of novel studies. The design stage consisted of the analysis of specificity of the MIP, synthesized from the cross-linker and used five various functional monomers independently, in the presence of four different templates. The MIP from 1-vinylimidazole, imprinted by 4-hydroxyphenylacetic acid, revealed the highest specificity in relation to 4-hydro-3-nitrophenylacetic acid, with an affinity factor equal to 3, and the highest selectivity from a group of structurally similar and biologically important biomolecules. The theoretical analysis revealed that electrostatic interaction between the analyte and the polymer matrix enhanced selectivity. The physicochemical characterization showed the specific surface area of the MIP as being equal to 368.6 m2 g−1, and the presence of nitrogen atoms at the level of 6.80% wt., confirming the monomer residue in the material structure. The MIP was applied in the solid phase extraction protocol, allowing for the analysis of 4-hydroxy-3-nitrophenylacetic acid in a human urine sample. Finally, the conversion of 4-hydroxyphenylacetic acid in human urine in nitrate and nitrite salts at low pH conditions revealed an almost twofold increase in 4-hydro-3-nitrophenylacetic acid to 775 ± 81 ng L−1. The results also confirmed the applicability of the new MIP sorbent for the purpose of analysis of low levels of analyte, present in the complex sample.

In this paper, magnetic molecularly imprinted nano-conjugates were synthesized to serve as selective sorbents in a model study of tyramine determination in craft beer samples. The molecularly imprinted sorbent was characterized in terms of morphology, structure, and composition. The magnetic dispersive solid phase extraction protocol was developed and combined with liquid chromatography coupled with mass spectrometry to determine tyramine. Ten samples of craft beers were analyzed using a validated method, revealing tyramine concentrations in the range between 0.303 and 126.5 mg L−1. Tyramine limits of detection and quantification were 0.033 mg L−1 and 0.075 mg L−1, respectively. Therefore, the fabricated molecularly imprinted magnetic nano-conjugates with a fast magnetic responsivity and desirable adsorption performance could be an effective tool for monitoring tyramine levels in beverages.

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